Process for making tertiary alkyl amides



Patented Feb. 15, 1949 PR- GCESS F03 MAKING TERTIARY ALKYL AMIDES Mortimer T. l'larvey, South-Orange, ,NiiJgand:

Solomon Caplan. New York, N;-Y.; assign'ors to j Harvel Research Corporation,-=a corporation oi:

New .lersey No Drawing. Application October 12, 1946, 4

Serial No. 702,890

'7 Claims.

The present invention relates to chemical compounds andto methods and steps of making and using the same.

The present application is a continuation in part of our copending application Serial No. 347,493; filed July 25, 1940, now abandoned, which copending application was a continuation in part of our applications Serial No. 202,230, filed April 15, 1938, now U. S. Patent 2,2414%, .and Serial No. 217,220; filed July 2,- 1938, now abandoned.

The-compounds of the present invention are mono-tertiary-hydrocarbon amides which have the general formulaR-R in which R represents a tertiary alkyl group preferably having 4-6 carbonatoms and connected to and replacing a hydrogen atom of an-amino group of R which represents'an amide of a class consisting of oxamide, acetamide and-benzoic acid amide. Each of these various novel-compounds has the radicle CONHR in which R is a tertiary alkyl group preferably of4-to 6 carbon atoms.

The chemical compounds of the present invention can be made by reacting a tertiary hydrocarbon alcohol with one of said amides in the presence'of a mineral acid condensing agent such as" phosphoric acid, sulphuric acid and so on.

mustrauve examples of the products and the practice oi the methods of the presentinvention areas follows: 1

Example 1.About twelve grams of benzamide ai'idfiftee'ri cubic centimeters of concentrated sulphuric acid were shaken together at room temperature and therlheated a little to obtain a clear solution. This solution'was cooled to room temperature and about forty grams of tertiary butyl alcohol added gradually. The first five cubic centimeters of the tertiary butyl alcohol caused the mixture to solidify. Asthe remainder of the tertiarybutyl alcohol-is added, in small incremerits, the mixture was stirred and cooled to below about 25 C. and kept at room temperature. The completed mixture was allowed to stand overnight at room temperature and then neutralized by the addition of sodium hydroxide solution and filtered. The resulting white precipitate was washed with water, and dried. The melting point of this White precipitate is found to be 115 C. Said precipitate has said general formula R.R and specifically in which lt is CAI-ls.

Example 2.-About one-quarter mole- 2- tion about one-moler'l l grams) of tertiarybutyl alcohol was added gradually. The first addition of tertiary butyl alcohol caused precipitation-0f a :white solid and .as the addition ofthe tertiary butyl alcohol was. continued more of the white.

solid I separated until the. mixture was a. thick.

paste. There was also a separation OiWfiiBLllk soiuble liquid. The mixture wasleft to stand at room temperature... overnight, and, then poured into a solution oi. gramsoi NaOH in 5% 00.5

of water. Thisgave -a whiteprecipitate which wastfiltered .oit. The water. insoluble liquid also. gave a white solid .on evaporation. The com: bined solids. were. washed with water. and-dried. This product is. insoluble inwater but soluble. inv ethylether. Oxamideitself is insoluble in ethyl ether. Themeltingpointof.this. product is, 170. C. This product has saidgeneral formulaR R and specifically O=C'-NH O=OI-NH in which is CiHe:

' Example 3'."About"one hundredgrams of concentrated sulphuric acidwas added gradually,- i rismall portions. with cooling and-stirring, to about thirty grams of acetamide; A clear solution resulted; One hundred grams of tertiary butyl" alcohol were add'edgradually; with cooling; In both these coolings the temperaturewas-k-ept below ab0ut -25 0. and at room temperature.

The solution wasstill' clear'. This was allowedtostand'overnight and was then diluted by'pouring intoBUO cc. of water. The solution wasneutral' ized by the addition of calcium carbonate. The precipitated calcium--sulphate was removed by: filtration and the-filtratewasevaporated'by dryness andabatc'h ef-crystals remained from the evaporated filtrate: These; crystals werev shaken with ethyl alcohol; the miXtu-refiltered and the alcohol 1 removed from this second filtrate; by evaporation in an oven at C. fIheresu'lting crystalline mass is water soluble and has a melt; ingpoin-t of 63 C. The melting point of [acet amide is 190. This product has said general. formula RR'- and specifically It is noted that in making the mixture of the amide and sulphuric acid, the amide can be added to the sulphuric acid or' the sulphuric acid can be added to the amide, the addition being made gradually and the temperature kept below 70 C., also it is made of record and set forth as an advantageous step in the practice of the present invention that greater yields of the reaction prodnets are obtained by keeping the temperature of making the amide-sulphuric acid mixture and the addition of the tertiary alkyl alcohol to the amide-sulphuric acid mixture between about 15 C. and about 25 C. Also it is noted that the amide and the tertiary alcohol used can be mixed together first and the sulphuric acid added to this mixture gradually below 70 C. and preferably between about 15 C. and 25 C. Also, the amount ofsulphuric acid used is not limited to that given in the illustrative examples, and from about one-half mole to more than two moles can be used but the lower quantities of sulphuric acid give a lower yield of mono-tertiary-alkyl amide. Two moles of sulphuric acid in the illustrative example gave a substantial yield.

In the examples and in the general descriptions set forth above the reaction temperature is stated generally as being below about 70 C. and particular examples recite an operating temperature between about 15 C. and about 25 C. However, these temperatures are given as examples and not as limitations, even though it can be that certain narrow temperature ranges are optimum for the reaction of certain reaction materials, either for quantity of yield, minimum of other products of reaction, ease of operation, or generally for production on an economic basis.

' The upper limit for reaction in the liquid or solid the'reagent materials or the condensing agent is liquid. And it is intended that there is nothing herein, aside from specific statements in the claims, to limit the reaction temperature in the operation and practice of the present invention 5 and that there is nothing to limit certain of the claims from reading on reactions in the vapor phase. The invention broadly relates to condensation of said amides and tertiary alcohols to produce mono-tertiary-hydrocarbon amides.

The novel compounds of the present invention may be condensed with aldehydes or other compounds having reactive methylene groups to form resins. Generally 1 to 2 moles of an aldehyde such as formaldehyde may be reacted with one mole of any of these compounds to provide said resins. These novel compounds may be used in the compounding of rubber and may serve as accelerators in the vulcanization of rubber.

. We claim:

1. The method of making a mono tertiary hy- 4 benzoic acid amide, the alkyl group of said alcohol having 4-6 carbon atoms.

2. The method of making a mono tertiary hydrocarbon amide of the general formula R--R in which R represents a tertiary alkyl group of 4 to 6 carbon atoms and connected to and replacing a hydrogen atom of an amino group of R in which R represents an amide which comprises, at temperatures between about 15 C. and 70 C., reacting a tertiary alkyl alcohol with an amide selected from the group consisting of oxamide, acetamide and benzoic acid amide, in the presence ofa mineral acid, the alkyl group of said alcohol having 4-6 carbon atoms.

3. The method of making a mono tertiary hydrocarbon amide of the general formula R-R in which R represents a tertiary alkyl group of 4 to 6 carbon atoms and connected to and replacing a hydrogen atom of an amino group of R in which R represents an amide which comprises making a mixture of a tertiary alkyl alcohol an amide selected from the group consisting of oxamide,

acetamide and benzoic acid amide and sulphuric acid at a temperature between about 15 C. and about 70 (3., the alkyl group of said alcohol having 5-6 carbon atoms.

4. The method of claim 3 in which the temperature is maintained between about 15 C. and about 25C.

5. The method of making a mono tertiary hydrocarbon amide of the general formula R-R in' which R represents a tertiary alkyl group of 4 to 6 carbon atoms and connected to and replacing a hydrogen atom of an amino group of R in which R represents an amide which comprises, at temperatures between about 15 C. and 70 0., reacting a tertiary alkyl alcohol with benzamide in the presence of a mineral acid, the alkyl group of said alcohol having 4-6 carbon atoms.

6. The method of making a mono tertiary hydrocarbon amide of the general formula RR in which R. represents a tertiary alkyl group of 4 to 6 carbon atoms and connected to and replacing a hydrogen atom of an amino group of R in which R represents an amide which comprises, attem v peratures between about 15 C. and 70 C., reacting a tertiary alkyl alcohol with acetamide in the presence of a mineral acid, the alkyl group of said alcohol having 4-6 carbon atoms.

7. The methodof making a mono tertiary hydrocarbon amide of the general formula RR in which R represents a tertiary alkyl group of 4 to ing a tertiary alkyl alcohol with oxamide in the drocarbon amide of the general formula RR in the group consisting of oxamidgacetamide and 6 carbon atoms and connected to and replacing hydrogen atom of an amino group of R in which R represents an amide which comprises, at tern:

peratures between about 15 C. and 70 C. reactpresence of a mineral acid, the alkyl group of alcohol having 4-6 carbon atoms.

MORTIMER T. HARVEY. SOLOMON CAPLAN.

REFERENCES CITED The iollowing references are of record in the file of this patent:

Freund et al.: Ber. Deut. Chem. Ges., vol. 23,

' (1911), page 1205.

Brander: Rec. des Trav. Chim. des Pays Bas, vol. 37 (1918), pages 77, 79, 80, 8 1 and 8 2. 

